TW201136664A - Process for the surface-modification of flyash and industrial applications thereof - Google Patents

Abstract

Process for the surface-modification of flyash and industrial applications thereof have been described in this invention, which involve the new surface-sensitization, the new surface-activation, and the subsequent Cu or Ag coating of the as-received flyash particles in the conventional electroless bath. These new surface-modification processes offer efficient and cost-effective alternatives for the conventional processes which modify the surface of flyash particles with the costlier Sn-Pd catalyst-system. The flyash processed with the new surface-modification processes is also suitable for more number of industrial applications relative to that processed with the costlier Sn-Pd catalyst-system. The as-received flyash particles, processed via new surface-modification processes, find the industrial applications such as the conductive filler for manufacturing the conducting polymers, paints, adhesives, sealers, and resins used for the EMI shielding of the electronic devices, in the lead-based composites used in the automobile industries, and as a catalyst to purify the industrial waste-water by decomposing longer chains of organic molecules into smaller ones.

Description

201136664 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface modification method for fly ash and its industrial application. More particularly, the present invention relates to a surface modification method for fly ash, and to conductive polymers, paints, adhesives, sealers used in the automotive industry and catalysis. ) Industrial applications on resins, and on lead-based composites. [Prior Art] Fly ash (solid and hollow, also known as cenospheres), is a waste by-product of thermal energy equipment, which contains environmentally harmful cerium oxide (Si〇2) and alumina (Αία3). It is associated with iron, calcium oxidation (CaO), magnesium, and toxic heavy metals (such as arsenic, lead, and cobalt) and causes disposal problems around the world. The primary shortcoming of such abandonment (4) is that there is still a lack of fly-ash-based creative value-added products for industrial applications. A secondary disadvantage of using such waste materials is that new methods that can be used to modify the surface of fly ash particles to make them suitable for industrial applications are still limited (see http://edugreen.ter.res.in/) Expi〇re /air/ flyash.htm). A new electroless plating method for depositing conductive metals such as copper (Cu) and silver (Ag) on the surface of fly ash particles has been described. The prior art requires the adsorption of tin (11) ions 201136664 (1) (Sn2+) to fly ash particles by stirring fly ash particles in an acidic water bath (known surface sensitization bath) with vaporized tin (II) (SnC12). On the surface of SnCl-y ~^ Sn~ + 2〇/·~ The carrier is stirred in an acidic aqueous solution (known surface activation bath) with vaporized and derogatory GUIhPbCl2) (Table I Μ Μ 7| , + surface The sensitized fly ash particles utilize Pd cluster stealing to activate the surface of the fly ash pole.

Sn2++ Pd2+ Pd^ Sn4+ (2) Next, 5 is coated with copper or silver by the activated fly ash particles in the well-known φ x , ", and the electric bond bath, and the surface of the buck is modified to Fly ash-based products for industrial applications, 兮羽Α & 5 Hai knows that the electroless plating bath is composed of dissolved metal precursors (t L, a * 丄, lanes such as nitrates, sulfates or metals) Gasification), stabilizer (such as; West rhh // XT τ sodium sulphate potassium ((NaK) C4H4 〇 6)), pH control agent (such as barium hydroxide G sodium (NaOH)) ' and reduction An aqueous solution of an agent such as a plate (HCHO) is used.

Cu2+ + 2e~ -» Cu° (3) can be deposited with mica, graphite, oxidized 2〇3), oxygen cut (5)〇2) and titanium dioxide (Ti〇) by reference to S. 2) On the particle, the (10) method is known as Sn_pd catalyzed weave with copper as a self-activator ([Please refer to the following documents: s ShuWa and s

Seal, Electroless Copper Coating of Zirconia utilizing Palladium Catalyst,,,J. Am. Cream. Soc. 86 (2)279-285 (2003) i S. Shukla, S. Seal, Z. Rahman, and K. Scammon, “ Electroless Copper Coating of Cenospheres using Silver Nitrate Activator”, Mater. Lett. 57, 151-156 (2002), J. 201136664

Akesson, S. Seal, S. Shukla, and Z. Rahman, "Copper Copper Plating Process Control by SEM'', Adv. Mater. Processes (AMP) 160(2), 33-35 (2002); S. Shukla, S. Seal, S. Schwarz, and D. Zhou, "Synthesis and Characterization of Nanocrystalline Silver Coating of Flyash Cenosphere Particles by Electroless Process', J. Nanosci. Nanotech. 1, 417-424 (2001); S. Shukla, S. Seal, J. Akesson, R. Oder, R. Carter, and Z. Rahman, "Study of Mechanism of Electroless Copper Coating of Fly-Ash Cenosphere Particles", App. Surf. Sci. 181(1-2) 35 -50 (2001)]. A third major drawback of the prior art is that conventional tin-lead catalyst systems are very expensive. A fourth major disadvantage of the prior art is that there is no alternative to the ability to sensitize the surface of the fly ash particles by coating them with metals such as copper and silver. A fifth disadvantage of the prior art is that there is no alternative to the ability to activate the surfaces of fly ash particles by coating them with metals such as copper and silver (see D. Deonath and PK Rohatgi, "Cast Aluminium Alloy" Composites Containing Copper-Coated Ground Mica Particles”, J. Mater. Sci. 16(6), 1599-1606 (1981); W. Lu, VS Donepudi, J. Prakash, J. Liu, and K. Amine, “Electrochemical And Thermal Behavior of Copper Coated Type MAG-20 Natural Graphite”, Electrochim. Acta 47(10), 1601-1606 (2002); JF Silvain, JL Bobet, and JM Heintz, “Electroless Deposition of Copper onto Alumina Sub-Micronic Powders And Sintering", Composites A 33(10), 6 201136664 1387-1390 (2002); Y. Kobayashi, Υ. Tadaki, D. Nagao, and M. Konno, “Deposition of Gold Nanoparticles on Silica Spheres by Electroless Metal Plating Technique J. Colloid Interface Sci. 283(2), 601-604 (2005); K. Gopakumar, C. Pavithran, and PK Rohatgi, “Preparation of Copper Coated Titania Particles for Co Mposites", J. Mater. Sci. 15(6), 1588-1592 (1980); K. Gopakumar, TP Murali, and PK Rohatgi, "Metal-Shell Char Particulate Composites using Copper Coated Particles", J. Mater. Sci 17(4), 1041-1048 (1982); KGK Warrier and PK Rohatgi, "Mechanical, Electrical and Electrical Contact Properties of Copper Titania Composites", J. Powder Metall. 29(1), 65 (1986)]. SUMMARY OF THE INVENTION In view of the many deficiencies of the prior art, it is a primary object of the present invention to provide a surface modification method for fly ash and an industrial application thereof. Another object of the present invention is to modify the surface of fly ash particles by a new surface sensitization method by sol-gel coating of titanium dioxide (Ti02) photocatalyst, which can be used for copper such as fly ash - or Silver-coated and industrial applications as catalysts for purifying industrial wastewater by degrading longer chain organic molecules into smaller molecules. Still another object of the present invention is to deposit a metal cluster (such as copper (Cu 'self-activator), silver (Ag), wrong (pb), gold (Au), 201136664 I white (Pt) or any kind of shellfish. The surface of the titanium dioxide (Ti〇2)-coated fly ash particles is modified by a new surface activation step. A further object of the invention is to use fly ash particles via conventional electroless plating methods. The surface of the fly ash particles is coated with copper (Cu) or silver (Ag), which are surface sensitized and surface activated by a new surface modification method, which can be used in various industrial applications. For example, the manufacture of lead (Pb)-based composites for the automotive industry, as well as conductive polymers, coatings, adhesives, sealants, and electromagnetic interference (EMI) shielding used by resins for electronic devices. The present invention provides a surface modification method for fly ash and its industrial application. In the present invention, the original as-received flyash particles are first passed through the / gluto-gel ( Use burnt oxide _ precursor dissolve Surface sensitization is carried out by coating with titanium oxide (Ti〇2) in an anhydrous alcohol medium. Then, by exposure to continuous ultraviolet (uv) radiation in an aqueous solution containing metal ions, the surface is sensitized. The particles, the surface sensitized fly ash particles are surface-activated by depositing metal clusters (/M,), where Μ can be copper, silver, gold, fine, or any precious metal. The electroless plating bath coats copper or silver on the surface activated fly ash particles. In one embodiment of the invention, a method for surface modification of fly ash, wherein the method comprises the following steps: In the surface sensitization bath, the fly ash is given in an anhydrous 2 propylene solution (Poly) in the presence of n-propyl titanium (IV) acrylate 201136664 (Ti(〇C3H7)4) (0.0:Ul 〇M). Particles (1〇_5〇g.L_i); 11 simultaneously prepared a solution with anhydrous 2-propanol (1〇〇_5 〇〇 and ^) where the water is relative to the molar concentration of ☆ Ti(〇C3H7)4 The final ratio falls within the range of 2 to 15. The solution prepared in the step (ii) is added dropwise to the solution prepared in the step (1). In the float, the final ratio of +2_propanol to fly ash falls within the range of 25-100 ml g·, iv is stirred as the suspension obtained in step (iii) for 2-6 hours; v via filtration The particles obtained in the step (iv) are separated from the solution and dried in an oven at 8 〇 9 (drying at rc for J) to obtain a fly from the amorphous-titanium dioxide (Ti〇2). Ash particles; vi calcined at a temperature in the range of 400_60 (rc) as in the second step (v) coated with amorphous-titanium dioxide (with 〇2) flying 2 sub-period range of hours During the period, a fly ash particle coated with crystal-titanium dioxide (Ti〇2) is obtained; νϋ is in a surface activation bath, and an aqueous solution having a metal salt (pH~10-12, using an aqueous Nh4〇h solution (25_28) %) and the obtained fly ash particles sensitized as the surface obtained in the step (vi); continuously subjected to continuous ultraviolet light (UV), visible light or solar radiation as obtained in the step (vii) The suspension lasts a period of 201136664 between 4-6 hours to allow metal cluster deposition The surface is sensitized fly ash particles; ix is separated by filtration from the activated ash particles obtained in step (viii), followed by washing with distilled water several times to remove undesired ions from the surface X is a conventional electroless plating bath (containing sodium hydroxide (NaOH) (5-15 gL-i), potassium tartrate (NaKC4H4〇6) (3〇6〇gL-i) and metal salts (1_1〇) The surface of the g L·" aqueous solution is stirred as activated fly ash particles obtained in step (ix); XI slowly 30-40 wt.% furfural (hch〇) (5-20 ml. Li) is added as a reducing agent to the solution obtained in the step (χ); y xii is continuously stirred as the suspension obtained in the step (xi) until the first dark blue solution fades or becomes completely transparent; xiii passes through The metal-coated fly ash particles obtained in the step (χϋ) are separated from the suspension and dried in an oven at 80-9 (TC for 1 〇 to 12 hours to obtain a surface modification). Quality fly ash. In another embodiment of the present invention, a method of depositing titanium dioxide (Ti〇2) on the surface of fly ash particles for surface sensitization is selected from the group consisting of wet chemical processes (wet_chemical process) ) ' includes co-precipitation, sol-gel, hydrothermal, and microemuision; or any physical method, including sputtering, chemical steaming 201136664 gas deposition (chemical Vapor dermdH, P〇Sltl〇n), and thermal evaporation. In still another embodiment of the present invention, a ten-preferential sol-gel method deposits titanium dioxide (Ti〇2) on the surface of the fly ash particles. In a more specific embodiment of the invention, the titanium dioxide (Ti〇2) coated on the surface of the fly ash particles is confirmed by measuring and comparing the photocatalytic activity of the original and surface sensitized fly ash particles. Its presence, which relates to the rate at which methylene blue (MB) dye is decomposed in aqueous solution by continuous ultraviolet light (UV exposure), which is considered as a quantity of titanium dioxide (Ti〇2) deposited via sol-gel. In still another embodiment of the present invention, the metal salt used in the surface activation step is selected from the group consisting of copper (Cu), silver (Ag), lead (pd) 'gold (An), platinum (Pt) or any other precious metal nitrate, gas salt or sulfate. L In yet another embodiment of the invention, in view of surface activation, the steel (Cu) and the silver (Ag) metal salts. In a further embodiment of the invention, copper (Cu) and silver (Ag) metal salts (CuS〇4 and AgN〇3) are preferred in the case of Cu and Ag coating in conventional electroless plating baths. In still another embodiment of the present invention, the metal salt concentration in the step (vii) is in the range of 0.1 to 1.0 g. In another embodiment of the present invention, wherein the radiation used in the step (viii) is continuous ultraviolet light (UV) (λ = 200-400 nm), visible light (λ = 400-800) Nm) or sunlight (in = 200-800 201136664 nm). In still another embodiment of the invention, the surface-modified fly ash obtained as in step (xUi) comprises (a) fly ash particles (b) Photocatalyst for surface sensitization, selected from zinc oxide (ZnO), tin oxide (Sn〇2), titanium dioxide (Ti〇2), zinc sulfide (ZnS), cadmium sulfide (Cds) or any other a group of semiconductor materials; (4) a metal cluster (OHO wt.%) for surface activity 7, deposited on surface sensitized fly ash particles, selected from copper, silver, gold, platinum or any other precious metal The group formed by the group and the group selected from the group consisting of copper and silver are in another specific example of the it's 'the surface of the modified \ ° Haifei ash particle is composed of yttrium oxide (Si〇2) (40-50 (c^mr^(Al2〇3) (40.50%), the oxide compound of the dance constitutes the defeat / 〇) and the bismuth (Ti〇2) (2 ·4%%) Mixed fly ash In another specific example, the surface is modified to be too solid or hollow (hollow microbeads). Fly ash, where preference _f 1 , the surface is modified Photocatalyst - Titanium oxide (Tl〇2) as fly ash for surface sensitization = = another specific example, the surface is modified to be smaller and deviate to degrade the longer chain organic molecules A knife is used to purify industrial wastewater. 201136664 In still another embodiment of the present invention, the surface is used for manufacturing electromagnetic conductive materials, coatings, adhesives, and resins for electromagnetic interference of electronic devices. (EMI) shielding, ^ and the industrial application of the compound-based compound in the vehicle industry. In still another embodiment of the present invention, the change in surface morphology, surface chemistry, and surface texture of the surface modification method of the fly ash particles is performed by scanning electron microscopy (SEM), 1 shot separation analysis. (EDX), X-ray photoelectron spectroscopy (xps) and X-ray diffraction (XRD) are used for monitoring. In still another embodiment of the invention, the modified fly ash of the surface is electrically conductive, and the original fly ash is non-conductive. [Embodiment] The present invention provides a surface modification method for fly ash, as shown in Fig. 1. Block diagram, and its industrial application. The method comprises sensitizing the surface of the fly ash particles by stirring 10 to 50 gu of fly ash particles in a surface aging bath, wherein 100-500 ml of anhydrous water is mixed dropwise with 0.01·1 〇M isopropanol (ιν) 2-propanol solution and 100-500 ml of 2-propanol aqueous solution (foot = 2_15, wherein the ratio of water to Τί(〇^7) 4 is expressed since the ratio). The resulting suspension was stirred for 2-6 hours. Next, the particles were separated from the solution by filtration and dried in an oven at 80-90 ° C for 1 〇 12 hours. The fly ash particles coated with amorphous-titanium dioxide (Ti〇2) are then burned under voodoo 2011 201136664 for 1-4 hours to obtain crystallization-titanium dioxide (Ti〇2) coated fly ash particles, as in This is shown in Figure 9b. Then, the surface sensitized fly ash particles are passed through an aqueous solution containing 〇.1-1.0 gL-i nitrate steel (n) (cu(N〇3)2.3H2〇) or silver nitrate (AgN03) (pH~) The surface activation bath of 1〇_12, obtained using an aqueous NH4〇H solution, was agitated to be surface-activated. Subjected to continuous ultraviolet (UV) (λ = 200_4 〇 0 nm), visible light (λ = 400-800 nm) and solar radiation (λ = 200_800 exposure, continuous stirring of the suspension for 4-6 hours) to make Cu or Ag Clusters> accumulate on the surface of the fly ash particles. The surface is activated by separating the activated fly ash particles and washing with water several times to remove undesired ions from the surface as in Figure 9c Shown. For coating copper (or silver) 'with sodium hydroxide (NaOH) (5-15 gL-i), NaKC4H4〇6 (30-60 gL-i) and copper (II) sulfate pentahydrate (II) 〇4.5H2〇, 1-10 gL-i) of the aqueous solution of S known non-electrical mineral bath to mix 5 new surface activated fly ash particles. 5-20 claws 1.1^ 3〇-4〇wt.% HCH is slowly added to the suspension as a reducing agent. The resulting suspension is continuously stirred until the initial dark blue solution fades or becomes completely transparent. Next, the copper coated fly ash particles are separated by filtration. Open and dry in an oven at 80-10 CTC overnight, as shown in Figure 9d. The following examples are merely illustrative of the steps of the present invention, and It is not to be construed as limiting the scope of the invention. 201136664 Example 1 In this example, Ti(OC3H7)4 and anhydrous 2-propanol were purchased from Alfa Aesar (trade name of India); NH4OH (content 25- 28 wt.%), NaKC4H4〇6, and silver nitrate (AgN03) are purchased from SD Fine Chemicals Ltd. (India); Cii(N〇3)2.3H2 is purchased from CDH Analytical Reagent (India) ); sodium hydroxide (NaOH) (content 97%) is purchased from

Hi Media Laboratories (india company); CuS04.5H20 (content 98.5%) is purchased from Nice Laboratory Reagent (india company); and HCHO (37-41 w/v 〇/〇) is purchased from Nice Chemicals ( Indian company). The fly ash particles in powder form were obtained from the Unicorn Thermal Power Plant (india company in Tamina Du). All chemicals and powders were used as they were without any further purification. In the new sensitizing bath (composed of 125 1111 anhydrous 2-propanol solution with 〇. Μ (final concentration) 1^(〇03117) 4), the fly ash particles of 5. g were mixed. 125 ml of a solution of 2-propanol and water (feet = 2) was added dropwise to the suspension, and the resulting suspension was stirred for 4 hours. The particles were then separated from the solution via filtration and dried in an oven at 80 ° C for 12 hours. The fly ash particles coated with amorphous-titanium dioxide (Ti〇2) were then calcined at 4 ° C for 2 hours to obtain fly ash particles coated with crystal-titanium dioxide (Ti 2 ). Next, via a new surface activation bath (aqueous solution containing 48.48 g Cu(N03)2.3H2 ’], pH ～10.5, using water 201153664

Nh ^ oh "grain solution" was stirred to surface-activated surface sensitized, bonfire particles to continuous ultraviolet (UV) radiation (λ = 200-400 rnn) exposed continuous fresh liquid for 4 hours, so that Copper as a self-activator is deposited on the surface of the fly ash particles. The surface activated particles are separated by filtration and washed several times with distilled water to remove undesired ions from the surface. Next, the fly ash particles activated on the surface of the surface of the quaternary electroless mineral bath containing NaOH (10 gL 1 ), NaKC4H4 〇6 (5〇gL-y and CuS04.5H20 (4.0 gL ^). The HCHO of 1 is slowly added as a reducing agent to this suspension, and the resulting suspension is continuously stirred until the initial dark blue solution fades or becomes completely transparent. The Cu-coated fly ash particles are then passed through. It was separated and dried overnight in an oven at 8 ° t. The surface morphology and particle size distribution of the original fly ash particles and the copper-coated fly ash particles were measured using an electron microscope (S l JSM-5600LV, Japan) a date) is measured at 15 kV; the total chemical composition is EDX analysis. The different phases present in the original fly ash particles and the copper coated (four) fly ash particles are χ-ray diffraction ( XRD) (Phillips 'Japan) to identify. Wide-spectrum. Scanning ray diffraction (XRD) analysis typically uses Cu Ka X-radiation (in = ^.542 A) in the range of 1 〇 8 〇. Carry out. After new surface sensitization and surface activation steps, fly ash particles Surface chemistry

Change 疋 using X-ray photoelectron spectroscopy (xps) (VG

Tech ESCA 3000, UK) Under the ink force of 1〇·9 Torr, the 201136664 was measured with Mg Ka X-radiation (1253 6 eV, line width 〇7 6” at 2〇〇w of electricity C. The fly ash particles are removed after each step of the xps analysis to understand the process of the steel coating of the fly ash particles. The full spectrum and the high resolution narrow energy spectrum are both 5 〇 eV electrons = 55 The sweep angle is recorded to achieve maximum spectral resolution. Narrow energy spectra and high resolution scans are performed for titanium (2p) and copper (2P3/2) ^ to understand these elements during the new surface modification process. Changes in oxidation state. Narrow energy spectrum scanning uses the peak-fit software (XPSPEAK 41) to solve the convolution to show the different forms of titanium and copper present on the surface of the fly ash particles. Gold (Au) 4f7 " at 84.0 The binding energy (BE) at ±〇·ι eV was used to correct the BE scale of the spectrometer. Use the BE scale of the hydrocarbon 4 in the exogenous carbon spectrum to inspect C (Is) BE at 284.6 eV to carefully exclude any The charge displacement generated by the sample buckle. Execute the Gauss/Luoren sub-peak table after removing the background. Nonlinear least square curve fitting method. It was confirmed by T that a titanium dioxide (Ti〇2) coating exists after surface sensitization of fly ash particles, by continuous stirring and exposure to continuous ultraviolet (UV) radiation (λ = 200-400). The photocatalytic activity of MB dyes in aqueous solutions containing different powder particles was monitored under nm) to study the photocatalytic activity of the original and surface-sensitized fly ash particles. The MB dye of 7 5 was completely dissolved in 75 ml of distilled water.

The original and surface sensitized fly ash particles of 0.4 g.L·1 were dispersed to prepare two different suspensions. The suspensions were corrected by stirring in the dark (not exposed to any of the radiation) for a period of hours to stabilize the surface adsorption of the MB 201136664 dye. Under continuous magnetic stirring, a stable aqueous suspension was irradiated with continuous ultraviolet (UV) light using a Rayonet photoreactor (Netherlands) containing a 15W electron tube (Philips G15T8) as a continuous ultraviolet (UV) source. UV) The source emits continuous ultraviolet (uv)-light shots with a wavelength range of 200-400 nm (corresponding to the optical energy range of 3.07-6.14 e). After exposure to continuous ultraviolet (uv) radiation, 3 ml of the suspension was taken from a continuous ultraviolet (uv) tank at intervals of 30 minutes for a total of 150 minutes of continuous ultraviolet (uv) radiation exposure to obtain continuous Ultraviolet (UV) visible light absorption spectrum. Using a centrifuge (R23, Remi Instruments India

Ltd. India Company) filtered the particles from the sample suspension, which was examined using an ultraviolet (uv) visible light spectrometer (Shimadzu, UV-2401 PC' Japan) to study the decomposition of the MB dye. The absorption spectrum of the MB dye solution was obtained as a function of continuous ultraviolet (uv) radiation exposure time in the range of 200-800 nm. The absorption peak (A) intensity of the Mb dye solution at 656 nm is considered as a measure of the residual concentration of the Mb dye (C). The mb dye-soluble, night continuous ultraviolet (UV)-visible absorption spectrum of the powder without the addition of powder particles was also recorded as corresponding to the initial MB dye concentration (C.) before exposure to continuous ultraviolet (UV)-[§. Reference spectrum. Next, a standardized residual Mb dye concentration is obtained using a relationship having the following form, '201136664

C〇 ) MB (4)

A, th, ie: 〇J (, 5 (vm also carried out photocatalytic experiments without adding powder particles to confirm the stability of MB dye exposure to continuous ultraviolet (UV) radiation in the absence of fly ash particles. In this case, the initial mb dye concentration (C0) remains unchanged even after a total of 15 minutes of irradiation of the sample. A typical electron microscopy (SEM) photomicrograph of the original fly ash particles is presented in ® 2(4) Non-spherical and spherical particles can be seen in the FF image. The size of the spherical particles is estimated to fall within the range of 5' _. The χ-ray energy of a spherical particle is dissipated X) In Figure 2(b), most of the original fly ash particles appear to contain oxidized inscriptions (Al2〇3) (48% donated) and cerium oxide (Sl〇2) (48.Gwt.%) with trace amounts. CaQ (1.4 wt.%) and dioxin = titanium (Ti〇2) (2.6 wt.%). Electron microscopy (SEM) images of copper (Cu) coated fly ash particles are shown in Figure 3 (4). Under the ratio = (Fig. 4), it is clear that the shape of the Cu_ film is rod-like; (the long sputum and the visibility ~ 100-200 nm), not in the original fly ash particles. Observed: Standardized residual MB dye inversion = continuous ultraviolet light (U, function of exposure time: Table: obtained by sensitized fly ash particles, presented in Figure V:), The corresponding curve obtained for decision is in the middle....Continuous ultraviolet (uv) radiation exposure, noting the original fly) 201136664 Ash particles exhibit photocatalytic activity for decomposing MB dye in aqueous solution. Note surface sensitization The photocatalytic activity of the fly ash particles is higher than that of the original fly ash particles. The /: (4) of the original and surface sensitized fly ash particles is estimated to be 0.005 minutes 4 and 〇〇〇 8 points q. Therefore, Titanium dioxide (Ti〇2) on the surface of the original fly ash particles: the condensed coating will enhance its photocatalytic activity. Therefore, photocatalytic experiments confirmed the stirring of fly ash particles in the new surface sensitization bath after the fly ash particles Successful titanium dioxide (Ti〇2) coating on the surface ^ Alumina (A1203) Wide-energy-scanning x-ray on the surface of fly ash particles after new surface sensitization, surface activation, & Photoelectron spectrometer (XPS) analysis is shown in Figure 5. In Fig. 5(a), the broad spectrum scanning spectrum obtained from the surface of the original fly ash particles shows the presence of aluminum (A1), strontium (Si), calcium (Ca) and oxygen (〇) groups ( At the BE levels of 74 6 , 103.4 , 347 · 5 and 532.0 eV , there are corresponding white "Lu (2P), 矽 (2P), calcium (2p) and oxygen (1 s) peaks respectively. The surface of the original fly ash is mainly composed of mixed oxides of AW3, Oxidation (Si〇2) and Ca〇. After the new surface sensitization step (Fig. 5(b)), additional peaks due to Ti (2P) can be seen at the BE level of 459~. This implies that * after stirring the particles in a new surface sensitizing bath, the fly ash particles are coated with titanium dioxide (Tl〇2)' in agreement with the photocatalytic experiment (Fig. 4). Surface sensitized fly ash particles, when sand mixed in a new surface activation bath, showed a Cu (2ρ) peak at 935 eV (Fig. 20 201136664:), suggesting that the Cu family exists in fly ash. The grain, as well as the material comparison shows that in the new table: there is a decrease in the peak intensity, which is accompanied by the heart: flying 4 ^ on the surface of the sub. The surface-activated fly ash particles showed a decrease in the Tl (2p) peak intensity when the increase in Cu(2p) peak intensity was shown to decrease in the intensity of the Cu(2p) peak (Fig. 5(d)). The XPS analysis of the be ^ ^ spectral scan of Ti(2p) at 452_471 eV with new surface sensitization and surface activation ^' is shown in Fig. 6. For the original,: surface sensitization, surface activation and Cu-coated fly ash particles ^i^rT' 458" 458*3 ^ 457-9 ev^ ^ P3/2 BE level ' implies titanium dioxide (Ti 〇 2) is present on the surface of the flying particles. Changes in the intensity of Ti such as 2 peaks after different processing steps are also noted in Figure 6. Although the Ti (2?) peak was not detected in the Kuannongxiong scan analysis, it seems to suggest that there is a trace of the dioxide dioxide = the surface of the original fly ash particles (Fig. 6(4)). However, the intensity of Ti such as 2 peaks increases after the original fly ash particles are stirred in a new surface sensitizing bath (Fig. 6(b)) 'which is compared with the broad spectrum scanning analysis (Fig. 5(b)) and The photocatalytic experiment (Fig. 4) was consistent. After being exposed to continuous ultraviolet (UV) radiation in a new surface activation bath to agitate the surface sensitized fly ash particles (Fig. 6(c))' and subsequently in the conventional helmet plating bath (Fig. 6(d)) In the Ti2p3/2 peak intensity, a gradual decrease is noted, which is also related to the broad spectrum scanning analysis (Fig. 5(c) and 5(d)), 201136664.射聂ΐ ί: In the new surface activation bath is subjected to continuous ultraviolet light (UV) to illuminate the surface of the electroless mineral bath (4). The surface of the CU 2PV2 peak is in the 927-940 eV and w/r. The narrow-spectral scanning XPS analysis is presented in Fig. 7(4). The 解c:u2P3/2 spectrum's untwisted rotation shows that there are three sub-peaks at 932, 叮 and at the BE level of 935.1 6^/, and two appear in The surface of the fly ash particles. . And 7/U) 2 related. The relative amount of surface-activated fly ash particles (Fig. (4)) 'CU〇 appears to be more than Cu〇 and Cu(OH)2. However, 'three CUs after the surface-activated particles are given in the conventional electroless mineral bath. The amount of niobium is increased relative to Cu(R) and Cu(〇H)2. Therefore, broad-spectrum scanning and narrow-spectral scanning xps analysis confirmed that the original fly ash particles were successfully coated with copper via a new surface sensitization & surface activation step. Titanium dioxide (Ti〇2) is a semiconductor with a wide band gap (~3 〇_3 2 eV) that requires continuous ultraviolet (uv) radiation exposure at the appropriate wavelength to produce an electron-hole pair. If the half-life of electron-hole pairs produced by continuous ultraviolet light (uv) is high, they may escape the particle surface and participate in the redox reaction. Conventionally, this method has been applied to the photocatalysis using titanium dioxide (Ti〇2), which decomposes longer-chain organic molecules (present in air or water) by subsequent formation of 〇H radicals and 〇H radicals. The smaller molecule is as outlined in Figure 8(a). Conversely, in this embodiment of the invention 22 201136664 'electron-hole pairs generated by continuous preparation of external light (UV) radiation exposure in semiconductor titanium dioxide (Ti〇2) have been applied by means of reduction intermediate The copper complex (such as [Cu(NH3)2] + ) surface-activates the fly ash particles with Cu clusters (Fig. 8(b)). [Cu{NH3)2T+e- -> Cu\a(,x)+2NHhaq)(9) Therefore 'in this new step of surface activation, titanium dioxide (Ti〇2) light coated by sol-gel The catalyst is effectively applied as a new surface sensitizer by continuous ultraviolet (UV) radiation exposure, and Cu is used as a self-activator to obtain a Cu coating of fly ash particles in a conventional electroless plating bath. Through the new surface sensitization and surface activation steps, the entire route of the copper coating of the original fly ash particles is summarized in Figure 9. The value was 2 and the calcination temperature was 4 Torr. (In the case of the original fly ash particles, the surface is sensitized in a new surface sensitizing bath to obtain sol-gel coated crystalline titanium dioxide (Tic, 2) (Section 9(a) and 9(b) Fig.) As a result, when the surface sensitized fly ash particles are subjected to continuous ultraviolet (UV) radiation exposure to a new surface activation bath, they are gel-sol coated semiconductor titanium dioxide ( An electron-hole pair is generated within Ti〇2) via the route described in Figure 8. The resulting electrons are then effectively used to reduce the intermediate copper (Cu)-complex to Cu(〇5) It is subsequently deposited on the surface of the fly ash particles. During the new surface 'tongue step, Cu ◦ and Cu(〇H) 2 are also formed on the surface of the fly ash particles together with the Cu 。. During the surface activation step, CU privately deposits this in the form of clusters (Fig. 9(c)) because titanium dioxide (Τι〇2) located under this layer can be detected in the broad 201136664 spectral scanning XPS analysis (section 5(c) Figure). In the conventional electroless plating bath, more cu〇 is deposited on the surface of the fly ash particles in a rod-like form (Fig. 3(b)). The copper coating is more continuous (Fig. 9(4)), which in turn reduces the amount of titanium dioxide (Ti〇2) detected in the X-ray photoelectron spectrometer (XPS) analysis (Fig. 5(d)). In this embodiment, new surface sensitization and surface activation methods have successfully demonstrated coating the surface of fly ash particles with copper via conventional electroless plating methods using copper as a self-activator. Example 2 In this example Mix 5 〇g of the original fly ash particles in a 125 ml anhydrous 2-propanol solution with 0.1 Μ (final concentration) Ti(〇C3H7)4. 125 ml of anhydrous 2-propanol and water The solution was added dropwise to this suspension. Two different suspensions were prepared for comparison at different values (2 and 5). The resulting suspension was stirred for 4 hours, and then the particles were filtered from The solution was separated and dried under 8 ° C for 12 hours. The fly ash particles coated with amorphous-titanium dioxide (Ti〇2) were then calcined at 6 ° C for 2 hours to obtain crystallized - Titanium dioxide (Ti〇2) coated fly ash particles. These surfaces are sensitized The fly ash particles are then surface activated by mixing in a new surface activation bath (aqueous solution containing 〇48 8 , pH~10.5, using an aqueous NH4〇h solution). The suspension is subjected to continuous UV Light (uv) radiation (λ = 200-400 ηιη) is exposed and continuously stirred for 4 hours, 24 201136664 to cause *silver as an activator to deposit on the surface of the fly ash particles. The particles are separated by filtration and washed several times with water to remove undesired ions from the surface. Next in the conventional electroless plating bath (containing Na〇H (i〇g ^), NaKC4H4〇6 ( The surface-activated fly ash particles were stirred in 50 gL-i) and CuS〇4 5h2〇 (4 〇 gl ^ in water). The HCHO of 乜ml.L-i was slowly added as a reducing agent to this suspension, and the resulting suspension was continuously stirred until the most open: dark blue solution faded or became completely transparent. The copper coated fly ash particles were then separated by filtration and then dried overnight in an oven at 80 °C. In the present embodiment, during the new surface sensitization step, amorphous-titanium dioxide (Ti〇2) coated fly ash particles were calcined at 600 C, which was slightly higher than that used in the examples. Temperature (4 ° ° C). Further, Ag clusters were used instead of the copper clusters (self-activators) as verified in Example 2 to surface-activate fly ash particles. [Ag(NH2)2] +e Ag°{ods)+2NH^a(/)(6) as for the original fly ash particles (after calcination at 600 ° C for 2 hours) and copper-coated fly ash particles The obtained broad-spectral scanning χ-ray diffraction (XRD) pattern using copper κα X-light shot (in = 1.542) in the 2-Θ range of 10-80° is presented in Fig. 10. In the first graph (a), it can be seen that the original fly ash particles (after calcination at 600 ° C) are essentially crystalline. By comparing with the JCPDS card # 83-0539, the diffraction pattern is identified corresponding to Diffraction peak of 矽(石25 201136664英). The diffraction pattern in Fig. 10(b) and Fig. 10(c), which is obtained by using copper-coated fly ash particles (they use two kinds) Different surface values (2 and 5) are surface sensitized), showing additional peaks corresponding to (Ul)Cu and (220)Cu, which are diffractions obtained by comparison with JCPDS card #04-0839 The pattern was identified (Fig. 10(d)). Therefore, χ-ray diffraction (XRD) analysis clearly shows the successful Cu-coating of the original fly ash particles using silver as the S activator. Because of the main peak (111)cu High strength, compared to fly ash particles with surface sensitization with r-value of 2, surface sensitized fly ash particles (expressed) with r value of $ may exhibit large copper plating Thickness (Fig. 10(b)). A typical electron microscopy (SEM) image of a spherical and copper-coated fly ash particle is presented in Figure u (a) Figure 1 and Figure U(b), where the virgin surface of the fly ash particles The heart is clearly visible because of the change in the copper bond. Copper-mineral film looks like Cu particles from spherical submicron size dip 200 崎)

to make. Fluorescence analysis of fly ash particles by copper-coated shovel (EDX is shown in Figure u(4), which shows additional peaks of steel when compared to peaks corresponding to fly ash particles in Figure 2(b) Therefore, the original particles were successfully surface-sensitized by (4) 2 and different R values, and coated with 60 CTC segmentation temperature in the case of silver as a catalyst: 实施 Example 3 The original fly ash particles in this example were surface sensitized with an R value of 15 26 201136664, calcined at 60 (TC under TC, and surface activated with silver (Ag). All other processing parameters were maintained similar to Example 2 The above-mentioned β observed the successful copper coating of the original fly ash particles under these treatment conditions, which is a color change in a few minutes by the known electroless plating bath (from the initial dark blue to completely transparent) To show that the presence of steel_coating was also confirmed by X-ray diffraction (XRD) analysis (Fig. 12). The diffraction pattern was observed to be similar to that shown in Fig. 1(b) and Fig. 2 Example 4 The original fly ash particles are also surfaced at a higher r value of 3 〇·15 〇. Sensitization. However, under these treatment conditions, it was noted that it, titanium (10) 2) powder formed, ... titanium dioxide = sterling homogeneous sink, can not be successful on the surface of fly ash particles via sol-gel: titanium oxide (Ti◦ phase film. The total two' can be successfully used as described above through the examples 2 and 3. The new surface sensitization of the present invention and the money of the present invention are on the surface of the original fly ash particles. The particle contains a sufficient amount of dioxin surface sensitization step on its surface. Weiwu), the main advantages of the invention can be skipped: Metal plating, special:,: A new way to sensitize fly ash particles The film is specially made of steel or silver metal film. I provides a new way to surface-activate fly ash particles to obtain 27 201136664 metal rhodium, especially copper or silver metal coating. ^ 3. For the surface sensitizer Sol-gel treated titanium dioxide (Ti〇2) provides a new application for the supply of fly ash as a 1-value product. ° 士士!/ Especially using a film of TiO2 as a photocatalyst: :-New in the form of fly ash particles A matrix (matrix) that purifies industrial wastewater by degrading organic molecules into shorter chain organic molecules. r Surface modification tt provides a new surface modification step for the fly ash by using an economically implementable and environmentally friendly new surface. clothes

Conductive polymers and coatings for shielding applications = the possibility of manufacturing O-resin. 2 agents, sealants and 6. Provide a possibility to re-use the fly ash that is harmful to the brothers with the bonus ring Lingyou-A'. 28 201136664 [Simple Description of the Drawings] Figure 1 presents a block diagram illustrating a new surface modification method involving new surface sensitization and surface activation methods to fly fly ash in conventional electroless plating baths. The surface of the particles is coated with a metal such as copper (Cu) or silver (Ag). 'R' is defined as the molar concentration ratio of the aqueous phase to Ti(OC3H7)4. Figure 2 shows a typical electron microscope (SEM) image (a) and EDX analysis (b) of the original fly ash particles. Fly ash particles are made up of

Oxide mixture of Si〇2 (40-50 wt.%), Al2〇3 (40-50 wt.%), Ca〇 (1_3 wt.%) and titanium dioxide (Ti〇2) (2_4 wt%) . σ Figure 3 shows the fly ash particles coated with Cu after sensitization (foot < and T = 400t) and surface activation (Cu as self-catalyst) in the electroless plating bath. Typical electron microscope (SEM) images at low (a) and higher (b) magnifications. The Cu-family rod growth was seen in (b). Figure 4 shows the normalized (♦) and surface sensitized () (foot = 2 and T = 40 (TC) fly ash particles, standardized residual mb dye concentration as continuous ultraviolet light (uv) _ light shot Typical changes in the function of exposure time (4) 'α and curve (b) of the first-order reaction rate constant velocity (&w) with m. Figure 5 shows the surface of the fly ash particles after a new surface sensitization and surface activation step Wide-spectral scanning xps analysis (岣 original; (b) surface sensitized (R==2 and T = 4〇〇t); (4) surface via 29 201136664 = (CU as self-catalyst); And (4) Cu-coated ore and particles. Figure 6 shows the use of a new surface sensitization and surface active ash particles to obtain a spin xps narrow energy spectrum scan P. 曰 (4) original; (b The surface is sensitized (feet = 2 and D = 〇; (4) the surface is activated (Cu as a self-catalyst); and (d) the Cu-coated fly ash particles. Figure 7 shows the use of a new surface The modified method of the fly ash particles obtained the solution back to the 35xps narrow energy spectrum scanning Cu 2p"2 spectrum. (4) The surface is activated (Cu as Catalyst) and (b) Cu-coated fly ash particles. In (4) and (b) towels, (1) Cu; (8) Cu〇; and (iii) Cu(〇H)2 〇... Figure 8 shows fork to continuous ultraviolet light (uv) radiation exposure using a semi-conductive titanium oxide (Ti〇2) photocatalytic route 0) and the use of sol-gel treated titanium dioxide (Ti〇2) as a new surface sensitizer for subsequent fly ash particles Surface activation and proposed route for Cu_mine film (b). Figure 9 presents a diagrammatic representation of a new surface modification method involving new surface sensitization and surface activation methods in electroless plating The surface of the fly ash particles is coated with a metal such as Cu*8 in the bath. (1) the surface of the original fly ash particles; (ii) the sol-gel coated titanium dioxide (Ti〇2) of the fly ash particles Surface (new surface sensitization steps are wide (iii) continuous ultraviolet light (uv broad radiation; (iv) metal clusters are deposited by continuous continuous ultraviolet (UV)-radiation exposure, where 201136664 can be Cu, Ag, Pd, Au, Pt or any other precious metal) (new surface activation step); (v) stirring in a conventional electroless plating bath After the activated fly ash particles, the Cu_ coating formed by the Cu group deposition. Fig. 10 shows the original (a) obtained after using Ag as a surfactant (after 600 (after calcination) and X-ray diffraction (XRD) analysis of Cu coated (b, c) fly ash particles. In (1)) and (c), at 60CTC calcination temperature, 2 and 5 scale values are used. In the new surface sensitization of fly ash particles, in (a), the peaks indicated as ·· represent the diffraction peaks corresponding to vermiculite (quartz) in the fly ash particles (matrix_ceramic). Figures 11(a) and 11(b) show the original and spherical

A typical electron microscope (sem) image of Cu coated fly ash particles. Red Cu-coated fly ash particles are sensitized in a conventional electroless plating bath (R = 2 and ., T = 60 (rc) and the surface is activated (used

The fly ash particles are obtained. (c) EDX analysis of & coated fly ash particles as shown in (b). X - Fig. 12 shows a x-ray diffraction (xrd) analysis of Cu-coated fly ash particles obtained using Ag as a surfactant. The calcination temperature of 6 ° C was applied to the new surface sensitization of the fly obtained with a value of 15. f [Key component symbol description] Benefit. *

Claims (1)

201136664 VII. Patent application scope: 1. A method for surface modification of fly ash, wherein the method comprises the following steps: i. in a surface sensitizing bath, having Ti(〇C3H7)4 (0.01-1.0 Μ The anhydrous 2-propanol solution (1〇〇_5〇〇ml) is stirred in the fly ash particles (10-50 gL-i>; u· simultaneously prepared with anhydrous 2-propanol (1 () 0_5 〇〇 ml And a solution of water in which the final ratio of water to the molar concentration of Ti(〇C3H7)4 (/foot,} falls within the range of 2 to 15; iii. The solution prepared in step (ii) Adding dropwise to the suspension prepared in the step (1), wherein the final ratio of 2-propanol to fly ash falls within the range of 25-100; iv. stirring as the suspension obtained in the step (out) 2_6 hours; v. The particles obtained in step (iv) are separated from the 'liquid by filtration and dried in an oven at 80-90 ° C for 10-12 hours to obtain amorphous _ Dioxide. Titanium (Ti〇2) coated fly ash particles; vi. Calcined in the range of 400_60 (rc) as obtained in step (V) The fly ash particles coated with amorphous_titanium dioxide (Ti〇2) are subjected to a period of 1-4 hours to obtain crystallized titanium dioxide (Ti〇2) coated fly ash particles; 32 201136664 Vii In the surface activation bath, the surface obtained in the step (vi) is mixed in an aqueous solution having a metal salt (obtained using an aqueous NH4OH solution (25-28 wt.%) at pH 〜10-12'). Sensitized fly ash particles; viii. continuous stirring by continuous ultraviolet (UV), visible or solar radiation. The suspension obtained in step (vii) lasts for a period of 4-6 hours to allow metal The clusters are deposited on the surface of the sensitized fly ash particles; ix. Separating the activated fly ash particles obtained in step (viii) by filtration, washing the water several times to remove undesired ions from the surface X. In the conventional electroless plating bath (containing sodium hydroxide (Na〇H) (5-15 蚪..., sodium tartaric acid (NaKC4H4O6) (30_60 gL·)) and metal salts (14〇gL-i Agitated in the aqueous solution) as the surface obtained in the step is activated by flying Particles; 'A slowly add 3 (M〇wt.%? ^(hch〇)(5_2〇ml.L i) as a reducing agent to the suspension obtained in step (8); xu. Stirring as a step The suspension obtained in (xi) is straight: the initial dark blue solution is tarnished or becomes completely permeable. xiii. The fly ash particles, which are all coated with money as in step (xii), are filtered from the suspension. The separation was carried out and 33 201136664 was dried in an oven at 80-90 ° C for 10-12 hours to obtain a surface modified fly ash. 2. The method of claim 2, wherein the method of concentrating titanium dioxide (Τι〇2) on the surface of the fly ash particles for surface sensitization is selected from the group consisting of: wet chemistry Methods, including coprecipitation, sol-gel, hydrothermal, and microemulsions; or any physical method 'including sputtering, chemical vapor deposition, and thermal evaporation. 3. The method of claim 5, wherein a sol-gel method is used to deposit titanium dioxide (Ti〇2) on the surface of the fly ash particles, and the patent target is 帛·一" The metal salt of VH) is selected from Cu, Ag, pd, and A. , Pt or any other precious metal nitrate, chloride or barium sulfate. 5. If the method of applying the patent range is the μ, the application step (the metal salt concentration of the second is in the range of 0.1-1.0 gL-1. 6) the method (vii) of the method of applying the patent scope, wherein In the case of surface activation, the method of Cu and the eight metal salts are referred to in the first item. Among them, Cu and Ag metal salts (CuS04 and AgN03) are preferred in the case of conventional electroless plating of Cu and Ag plating. 8·: A type of fly ash that has been modified by the method of the first paragraph of the patent scope, which contains (4) fly ash particle photocatalyst (5)-4 〇 ” for surface sensitization, selected (J 34 201136664 ZnO, Sn〇2, titanium dioxide (Ti〇2), Zns, cds or any other group of semiconductor materials; (4) metal clusters (3.0 wt. stone) for surface activation, deposition on the surface sensitized On the fly ash particles, selected from the group consisting of cu, Ag, Pd, Au, pt or any other precious metal, and (4) metal coating (1·(Μ〇wt %), 掸白于士广群.^ 9············································· ^ 5 Haifei ash particles are composed of a mixture of (40-50 wt.%), Al2〇3) 1-3 (1-3 wt.%) and titanium dioxide (i〇2) (2-4 wt.%). Composition:::: The modified fly ash on the surface of item 8 of the profit range, the n ash particles are solid or hollow (hollow beads). 11. If the scope of the patent application is changed, the surface of the member is modified. The quality of fly ash, its emulsified titanium (Ti〇2) as a light touch for surface sensitization ♦~ 12. As in the scope of the patent application, the product can be used as a fly ash for the surface modification of the surface. Degradation into smaller 2 is worse. The longer chain has 13. As in the scope of patent application:: to purify industrial wastewater. The product is used in the manufacture of eulogized/surface modified fly ash. Can be used as a conductive fill